Optimizing electronic states of Pd/WO3 nanofibers for enhanced catalytic reduction of hexavalent chromium with formic acid.

Through theoretical calculations, we show that integrating Pd with WO3 nanomaterials can trigger the interfacial electron transfer from Pd to WO3, thus upshifting the d-band center (εd) of Pd to optimize toxic hexavalent chromium (Cr(VI)) reduction. The elevated εd can derive stronger chemisorption capability toward crucial formic acid molecules, notably lowering the thermodynamic energy barrier and speeding up the kinetics process. In order to realize this concept, we synthesized unique Pd/WO3 nanofibers by loading Pd nanoparticles onto electrospun WO3 nanofibers through an in situ photodeposition technique. Extensive structural, morphological, and X-ray photoelectron spectrometer (XPS) characterizations confirm the successful formation of the above nanofibers. As anticipated, the as-designed Pd/WO3 nanofibers exhibit enhanced catalytic performance in the Cr(VI) reduction with a high turnover frequency (TOF) value of 62.12 min-1, surpassing a series of reported Pd-based catalysts. Such nanofibrous WO3-induced electronic modification of Pd with a high specific area leads to catalytic enhancement, providing a novel model for catalyst design.